CN103429797A - Dire-contact membrane anode for use in electrolysis cells - Google Patents
Dire-contact membrane anode for use in electrolysis cells Download PDFInfo
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- CN103429797A CN103429797A CN2011800605189A CN201180060518A CN103429797A CN 103429797 A CN103429797 A CN 103429797A CN 2011800605189 A CN2011800605189 A CN 2011800605189A CN 201180060518 A CN201180060518 A CN 201180060518A CN 103429797 A CN103429797 A CN 103429797A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/002—Cell separation, e.g. membranes, diaphragms
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
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Abstract
The present invention relates to an anode system for conventional electrolysis cells, a process for the production thereof and its use for the deposition of electrolytic coatings. The anode system is characterized in that the anode is in direct contact with a membrane which completely separates the anode space from the cathode space. This anode system is therefore a direct-contact membrane anode.
Description
The present invention relates to a kind of for the film anode architectures such as traditional electrolyzer, a kind of this film anode architectures method and its purposes in the electrolytic coating deposition of manufacturing.Undesirable anode oxidation process in not having the anodolyte district to work thereby this film anode architectures is characterised in that it to help avoid plating bath.
On the plastics of other metal or metal-coated membrane, to be called the metal or metal alloy of coating be a kind of technology of having established to electrochemical deposition, for improving quality, decoration and increasing surface-tolerant (Praktische Galvanotechnik, Eugen G.Leuze Verlag).The electrochemical deposition of this metal or metal alloy is used the anode and the negative electrode that immerse a kind of electrolyzer that electrolytic solution is housed to carry out usually.Apply voltage between these two electrodes (anode and negative electrode), metal or metal alloy will deposit in substrate (negative electrode).In some cases, by this structural modification, and provide a kind of electrolyzer of catholyte (electrolytic solution in cathodic area) and anolyte (electrolytic solution in positive column) that electrolytic solution is divided into by a kind of semi-permeable membranes.This substrate (negative electrode) is immersed and to be contained this and remain the catholyte of metal ion of deposition.While applying voltage, electric current enters catholyte via anolyte by this film.These systems can have been bought on market.Yet, in order to ensure flowing of electric current, use a kind of anolyte in positive column in all these systems.For these systems, the maintenance of this anolyte, analysis and maintenance need extra-pay.If the film in these systems has damaged, anolyte enters cathodic area and pollutes catholyte.In most of the cases, what therefore catholyte became can not use, and need to process in a kind of mode of costliness.The another one unfavorable factor is the increase of this anode electrolysis liquid zone space requirement, and this is not suitable for the commodity coating.As a result, in the situation that with regard to cost and time, a very high expense is arranged, these traditional systems just can be introduced into existing electrolyzer.
In the situation that a lot of electrolytic solution adopts is traditional, insoluble anode operates, undesirable anode oxidation process often occurs.In these cases, the metal existed in catholyte, complexing agent and organic additive are oxidized at insoluble anode surface in deposition process.Due to these oxidising processs, because the oxidation products formed has disadvantageous effect to electrolytic deposition, be limited the work-ing life of a lot of ionogen/electrolyte systems.In addition, organic or inorganic compound expensive, that exist with the brightening agent form is destroyed and replacement continuously at anode, and this represents a larger cost factor.In the situation that precious metal electrolytic solution, due to the fresh batch of material of needs or consuming time and expensive scavenging process, has produced extra large cost factor.
Purpose of the present invention, particularly, be to avoid these undesirable anode oxidation process in deposition process, and simplify existing film electrolysis system so that the present invention can directly apply to existing equipment and not need expensive retrofit work.
These and other the purpose that can obtain from prior art by obvious mode are completed by a kind of anode architectures of the theme that forms the claims in the present invention 1.The embodiment of this anode architectures is prescribed in claim 2-4.Claim 5 is for the applicable method of manufacturing anode architectures of the present invention.Claim 6-9 comprises the favourable purposes of anode architectures of the present invention in a kind of electrolytic process.Claim 10 is for a kind of electrolyzer that comprises anode architectures of the present invention.
A kind of anode architectures is provided, this anode architectures is configured to the electrolyzer that makes this anode architectures be suitable for depositing electrolytic coating owing to immersing simply in catholyte, wherein, after immersing catholyte, this catholyte separates by a kind of polymeric film and anode of the swelling that allows positively charged ion or negatively charged ion to pass through, and this polymeric film directly contacts and do not contact with negative electrode with anode, this anode architectures is very favourable but equally unexpectedly realized described target.That the selected arrangement of this anode makes it possible to is that fill by anolyte, positive column that usually be present in a kind of electrolyzer is reduced to a kind of anode, and this anode is by the sealing of a kind of polymeric film of swelling and contact with it.This causes the necessary anolyte of electrolysis to be removed fully.Except the effect of joint space-efficient, be further noted that till now and do not have undesirable oxidizing reaction or destructive side reaction to occur at this anode, this contributes to increase significantly the stability of electrolytic solution.Finally, also need be the additive described due to the material of needs especially introductory song still less, the use cost of electrolysis reduces.This does not anticipate according to prior art.Can be with reference to the information provided aspect the method for this direct contact membranes anode of preparation of the present invention in the application of anode about polymeric film.
About using the container that carries out electrolysis according to arrangement of the present invention, use is all possible (Praktische Galvanotechnik to the admissible any container of those of ordinary skill in the art, Eugen G.Leuze Verlag, the 5th edition 1997,93 pages of ff.).Although, using the corresponding substrate of metal refining or metal alloy as negative electrode, the anode used in the present circumstance is a kind of insoluble electrode.Those of ordinary skill in the art has enough understandings to this class anode.This anode can be by flat material (flat material=tinsel (metal anode)), board-like material (GLC anode, graphite anode), agglomerated material (http://de.wikipedia.org/wiki/Sintern) or expanded metal (by Umicore Galvanotechnik GmbH supply, anode used for electroplating) form.As insoluble anode, the anode that preferably uses those materials in lower group to form, this group is comprised of the following: the titanium of platinum plating, graphite, stainless steel, be coated with the titanium of iridium-transition metal mixed oxide, tantalum or niobium and special carbon material (" diamond-like-carbon " DLC, " vitreous carbon " GC) and the combination of these anodes.Particularly preferably be by iridium-ruthenium mixed oxide the Mixed Metal Oxide Coated Titanium Anodes that iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxide forms.More applicable anode can be at Cobley, purposes (the The use of insoluble Anodes in Acid Sulphate Copper Electrodeposition Solutions of the insoluble anode that A.J.et al. delivers in the acid copper sulfate electric depositing solution, Trans IMF, 2001,79 (3), 113 and 114 pages) in find.The shape of this anode can suitably be mated corresponding electrolysis purpose by those of ordinary skill in the art.Very particularly preferably be to use to be coated with titanium, niobium or the tantalum piece material of the mixed metal oxide insoluble anode material as direct contact membranes anode of the present invention.
To the admissible all films of those of ordinary skill in the art, can be used for as the possible polymeric film of the object of the invention, such as positively charged ion-or anion-exchange membrane (abbreviation ion-exchange membrane).While selecting these films, at first those of ordinary skill in the art will consider that only specific ion can pass through this film, and this film should have high receptivity so that this film has enough electroconductibility for treatment soln; And secondly, this film should be able to be set up and directly contact so that best current transfer can actually occur with the whole surface of anode ideally.All conventional ion conductive membranes that is called as ionic polymer are all the films that is applicable to this application.These are used in polymer dielectric film fuel cell or store battery usually.Example:
Polypyrrole film (Flintjer, B.; Jansen, W.:
Polypyrrol und Polypyrrol-Batterien.In:Praxis der Naturwissenschaften-Chemie, Jg.38,1989, the 3 phases, 7-11 page .);
Olefin polymer films (DE19826702A117.12.1998, Verfahren zur Herstellung einer Ionenaustauschermembran, die als Separator in einer Brennstoffzelle verwendbar ist, Solvay S.A., Brussels/Bruxelles, BE, Brunea, John A., Tavaux, FR)
Example: the TOPAS COC polymeric film obtained from the TOPAS prepolymer;
The sulfonated polystyrene film, perfluorination ionic polymer (PFSI film), S-PEEK, S-PSU, PSU-CI, ICVT film (Bipolarplatten f ü r Polymerelektrolyt Brennstoffzellen aus thermisch-und elektrisch
Thermoplastischen Kunststoffen, Rezeptierung, Herstellung, Charakterisierung und Anwendung; 2.4.1.4Die Membran pages30 33; The preparation of Ralf Kaiser ISBN978-3-8325-2033-5/ proton exchange membrane fuel cell membrane, World Science institute, engineering and technology 482008, Nilar Win, Mya Mya Oo);
Fluoridize/fluoridized sulfonated polymer films (PFSA film).Example: the Nafion film of E.I.Du Pont Company: Nafion N112, Nafion N115, Nafion N117, Nafion324, Nafion N424, Nafion NR211, Nafion NR212, Nafion N1110.
The Aciplex film of morning sun chemical industrial company.
The Flemion film of Asahi Glass company.
R.Fernandez: polymer data handbook, 1999, Oxford University Press, company, 233ff page (R.Fernandez:Polymer Data Handbook, 1999, Oxford University Press, Inc., Pages233ff);
Aryl polymer film (WIPO patent application WO/2001/064322, application number: PCT/EP2001/002311, publication date: September 7 calendar year 2001, date of application: March 1 calendar year 2001, Cui, Wei);
Polyetherketone film (polymer dielectric film and manufacture method thereof.EP0574791,HOECHST?AG,HELMER-METZMANN?FREDDY?DR）；
Polybenzimidazole membrane (
Http:// www.celanese.com/240501_powering_the_future-2.pdf);
Thermoplastic alkaline polymer film (EP0698300B1Polymer Brennstoffzelle, Fraunhofer-Gesellschaft zur
Der Angewandten Forschung EV 80636 Munich, Konstantin Ledjeff);
The perfluorinated sulfonic acid polymer film (for fuel cell to oxidation-stabilized polymer dielectric film, WIPO patent application WO/2008/025465, EP2007/007348, publication date: on March 6th, 2008, DAIMLERCHRYSLER AG);
Perfluorocarboxylic acid ester ionic polymer (Flemion Asahi);
Polymeric amide, polyamine, poly-(vinyl alcohol) film;
Perfluor phosphonic acids adipose membrane;
More applicable film, at " solid polymer electrolyte " Wiley1991, has description in this this book of Fiona M.Gray.
Preferably use the permeable film of positively charged ion.Particularly preferred polymeric film is the film in a kind of group of selecting freely fluoridize/fluoridized ionic polymer to form, very particularly preferably be the ionic polymer of fluoridize/fluoridized, sulfonation.These films have high electrolytic solution receptivity and therefore have low-down contact resistance, thereby significantly reduce electrolysis voltage.The further particularly preferred embodiment of these films be those in order to obtain high physical strength with the fiber reinforced film of Teflon optionally.
The present invention comprises a kind of method for preparing this direct contact membranes anode of the present invention equally.The method is characterized in that
I) allow this film pre-swelling in deionized water,
Ii) this preswollen polymeric film is directly applied to this anode and
Iii) this anode is enclosed in this polymeric film so that it is not soaked by catholyte.
Directly contact makes it possible to realize in a relatively simple manner electrolysis, and this mode is to be undertaken by between the negative electrode in a kind of catholyte (substrate) and anode, applying electric current.How those of ordinary skill in the art makes the pre-swelling of polymeric film (such as the information of manufacturer) if understanding.The swelling of this film is preferably carried out in subalkaline, deionized, warm water.
(fuel cell handbook (Handbook of Fuel Cells), Vol.3, Wiley2003,538ff page are known in the application of this film antianode from the fuel cell manufacture field by those of ordinary skill in the art; Http:// www.fz-juelich.de/ief/ief-3/MEA_Herstellverfahren/).Setting up is important with desirable direct contact of anode, preferably must between this film and this anode material, there is no gap.In the situation that combine closely very much between polymeric film and anode, favourable current flowing makes cell voltage lower.This film can be applied to anode with the form of polymkeric substance or with a kind of form of polymers soln.This preswollen polymeric film can be preferably applied by stacked, compacting, bonding and/or clamping.If use a kind of polymers soln, this ion selects layer to be applied to anode by immersion, casting, scraping blade coating, sputter, roll-in and/or silk screen printing.This polymers soln can be used as last one deck or uses as the caking agent between ion-exchange membrane and anode.
It is also important that polymeric film seals anode by this way, make while subsequently this anode being immersed to catholyte and do not have catholyte can enter this anode, the All Ranges of this anode immersion catholyte all is coated with polymeric film.The layer thickness of this film can be determined by normal experiment by those of ordinary skill in the art.It is guidance that those of ordinary skill in the art will be take the fact that the abundant inhibition of catholyte must meet ideal current flowing.
In a word, the mechanical endurance and the sticking power that direct contact membranes are fixed on by any way on anode to improve it are favourable.For example, this is by the support by electrolyte permeable and pressing device, film to be fixed on anode and to complete.This can, for example, by a kind of multilayered structure, occur on this film.This multilayered structure comprises the polymer layer of one deck sintering.This layer guarantees that the whole zone of this film and anode contacts and avoids the physical abuse to film.The porous polymer plate is applied to this sintered layer.These plates film-anode construction that this is whole forces together and is fixed.The good contact of this film and anode is always guaranteed by this multilayered structure, and provides protection to make film avoid physical abuse simultaneously.The mode of fixing this film itself that another is possible is that for example the Teflon fiber is reinforced it by adding supporting structure.Supporting structure as an alternative is possible (www.fumatech.com/Startseite/Produkte/fumasep/Ionenaustau sc hermembranen/) by other the monofilament of inert material manufacture or the yarn fabric of multifibres.
The present invention has also stipulated the purposes of direct contact membranes anode of the present invention electrochemical deposition metallic coating on decoration and mechanicals.According to purposes of the present invention, this decoration and mechanicals are preferably immersed to suitable catholyte, and generate enough electric currents in order to cause the deposition of this metallic coating between these goods and this anode.About this direct contact membranes anode or prepare the purposes that is applicable to similarly them of the further preferred embodiment that their method mentions.The temperature of deposition process is mainly determined by the catholyte used.Generally speaking, the temperature that film is still enough worked well in 1 ° of C-150 ° of C scope, 10 ° of C-100 ° of C preferably, and be very particularly preferably in the temperature range of 20 ° of C-80 ° of C.
This direct contact membranes anode of the present invention can be deposited in suitable substrate a lot of metals and metal alloy in common electroplating cell.Those of ordinary skill in the art will select electrolytic solution according to the metal that will deposit and metal alloy.Can mention by way of example the electrolytic solution of following applicable depositing noble metal and basic metal or their metal alloy, these precious metals and basic metal or the choosing of their metal alloy be silver freely, gold, palladium, platinum, rhodium, ruthenium, iridium, rhenium, copper, tin, zinc, iron, nickel, cobalt, chromium, manganese, molybdenum, tungsten, tantalum, thallium, bismuth, antimony, indium, gallium, lead, cerium, selenium, cadmium, samarium, vanadium, the group of tellurium and their alloy composition.
Particularly preferably be to use and be coated with titanium, tantalum or the niobium sheet material (referring to above) of the mixed metal oxide general embodiment as anode material.Thereby then by deionized water preswollen film be pressed on this metal sheet and so that it seals fully, the positive column of immersing catholyte do not soaked by catholyte.As a kind of replacement scheme, clamping is feasible equally.Subsequently this anode is immersed to a kind of catholyte, and cause electric current between negative electrode (substrate) and anode.
The present invention is similarly the deposition electrolytic coating a kind of electrolyzer is provided, and this electrolyzer has a negative electrode, a kind of catholyte and a kind of anode architectures as described above according to the present invention.The preferred embodiment of this electrolyzer can obtain from the top paragraph relevant to this anode architectures.
About favourable Application Areas, this direct contact membranes anode can be applied on the coating of parts in acidic copper electrolytes.In traditional coating process, use soluble anode.Due to the anodic current productive rate, higher than the cathodic current productive rate, copper is concentrated in these electrolytic solution.Therefore acidic copper electrolytes needs often to dilute so that operating parameters is not offset.Usually, additionally insoluble MMO anode (Mixed Metal Oxide Coated Titanium Anodes) is introduced in electrolytic solution to reduce the area of soluble anode, thereby the concentrated of copper do not occurred in these electrolytic solution.Yet organic brightening agent is destroyed by these anodes, and the very large loss that has produced expensive organic additive.If, by this soluble anode and this direct contact membranes anodic bonding, the anodic oxidation of the additive that these are expensive just can be avoided.
The Another application field is this direct contact membranes anode purposes in deposition chromium the electrolytic solution from containing Cr (III).In these electrolyte systems, the reaction that chromium is oxidized to chromium (VI) occurs in insoluble anode.This oxidation state toxicity of chromium is very large and be carcinogenic, and this electrolytic solution becomes unavailable.Due to the use of this direct contact membranes anode, this kinds of oxidation reaction can be avoided, and therefore the work sanitary condition improves, and the life-span of electrolytic solution has increased several times.
Use insoluble anode in the traditional method of depositing Pd-nickel.As time goes on, the complexing agent always existed is destroyed at these anodes, and Pd is converted into higher oxidation state.As a result, in this electrolytic solution, sedimentation rate (0.5Ah/l) after the very short time reduces, and the settled layer change is unavailable.The ordinary method that electrolytic solution is returned to the embryo deposit performance is to use activated carbon treatment.Yet this method is consuming time and expensive.When being used in palladium-nickel electrolyte by this direct contact membranes anode, these oxidising processs can be avoided, and significant prolongation in the work-ing life (> 20Ah/l of this electrolytic solution).
Other electrolyting precipitation process can benefit equally from use anode architectures of the present invention.In addition, this novel anode architectures easily operates than the traditional system that the negative electrode and positive electrode district separated is arranged.This system can be applied in existing electroplating device and not need a large amount of retrofit works.Except 100% electric current productive rate almost, because the Oxidative demage of additive reduces and occurs in anode without side reaction, the work-ing life that this direct contact membranes anode of the present invention makes electrolyte system, significantly (referring to above) increased.This does not anticipate in spendable prior art.
Accompanying drawing:
The structure of Fig. 1-a kind of conventional film battery
The structure of Fig. 2-direct contact membranes anode
Fig. 3-use a kind of electrolyser construction of direct contact membranes anode
Reference number:
1 negative electrode
2 anodes
3 ion-exchange membranees
4 anolytes
5 catholytes
6 electrolytic vessels
The mechanical protection of 7 antisitic defects
8 direct contact membranes anodes
Claims (according to the modification of the 19th of treaty)
1. anode architectures, this anode architectures is configured to the electrolytic plating pool that makes this anode architectures be suitable for depositing electrolytic coating owing to immersing simply in catholyte, wherein, after immersing this catholyte, this catholyte separates by a kind of swelling, polymeric film and anode that allow positively charged ion or negatively charged ion to pass through, and this polymeric film directly contacts and does not contact with negative electrode with anode
It is characterized in that
By this film, by a kind of multilayered structure, support and the pressing device by electrolyte permeable is fixed on this anode, guarantees like this good contact of this film and this anode.
2. anode architectures according to claim 1,
It is characterized in that
This anode is by flat material, and agglomerated material or expanded metal form.
3. according to claim 1 and/or 2 described anode architectures,
It is characterized in that
This anode selects the titanium of free platinum plating, graphite, stainless steel, be coated with the titanium of iridium-transition metal mixed oxide, be coated with the group that the combination of the tantalum of mixed oxide or niobium sheet material and special carbon material (" diamond-like carbon " DLC, " vitreous carbon " GC) and these materials forms.
4. according to the one or more described anode architectures in above claim,
It is characterized in that
Use a kind ofly to be selected from film in lower group as polymeric film, this group is comprised of the following: polypyrrole film, olefin polymer films, the Polystyrene Film of sulfonation, fluoridize/polymeric film (PFSA film) of fluoridized sulfonation, S-PEEK, S-PSU, PSU-CI, ICVT film, aryl polymer film, the polyetherketone film, polybenzimidazole membrane, thermoplastic alkaline polymer film, the perfluorinated sulfonic acid polymer film, perfluorocarboxylic acid ester ionic polymer, polymeric amide, polyamine, poly-(vinyl alcohol) film, perfluor phosphonic acid ester film.
5. the method for preparing one or more described anode architectures in the above claim of a kind of basis,
It is characterized in that
I) allow this film pre-swelling in deionized water,
Ii) this preswollen polymeric film is directly applied to this anode,
Iii) by this film, by a kind of multilayered structure, support and the pressing device by electrolyte permeable is fixed on this anode, guarantees like this good contact of this film and this anode, and
Iv) this anode is enclosed in this polymeric film so that it can not be soaked by catholyte.
According to the one or more described anode architectures in claim 1-4 decorate and mechanicals on the purposes of electrochemical deposition metallic coating.
7. purposes according to claim 6,
It is characterized in that
This decoration and industrial goods are immersed to suitable catholyte, and generate enough electric currents in order to deposit this metallic coating between these goods and this anode.
8. according to claim 6 and/or 7 described purposes,
It is characterized in that
This sedimentation is carried out in the temperature range of 1 ° of C-150 ° of C.
9. according to the one or more described purposes in claim 6-8,
It is characterized in that
Select a kind of can metal refining or the catholyte of metal alloy as catholyte, these metals or metal alloy choosing be silver freely, gold, palladium, platinum, rhodium, ruthenium, iridium, rhenium, copper, tin, zinc, iron, nickel, cobalt, chromium, manganese, molybdenum, tungsten, tantalum, thallium, bismuth, antimony, indium, gallium, lead, cerium, selenium, cadmium, samarium, vanadium, the group of tellurium and their alloy composition.
10. for depositing the electrolyzer of electrolytic coating, comprise a negative electrode, a kind of catholyte and according to the one or more described a kind of anode architectures in claim 1 to 4.
Claims (10)
1. anode architectures, this anode architectures is configured to the electrolyzer that makes this anode architectures be suitable for depositing electrolytic coating owing to immersing simply in catholyte, wherein, after immersing catholyte, this catholyte separates by a kind of polymeric film and anode of the swelling that allows positively charged ion or negatively charged ion to pass through, and this polymeric film directly contacts and do not contact with negative electrode with anode.
2. anode architectures according to claim 1,
It is characterized in that
This anode is by flat material, and agglomerated material or expanded metal form.
3. according to claim 1 and/or 2 described anode architectures,
It is characterized in that
This anode selects the titanium of free platinum plating, graphite, and stainless steel, be coated with the titanium of iridium-transition metal mixed oxide, the group that the combination of tantalum or niobium and special carbon material (" diamond-like carbon " DLC, " vitreous carbon " GC) and these materials forms.
4. according to the one or more described anode architectures in above claim,
It is characterized in that
Use and a kind ofly be selected from film in lower group as polymeric film, this group is comprised of the following: polypyrrole film, olefin polymer films, the Polystyrene Film of sulfonation, fluoridize/polymeric film (PFSA film) of fluoridized sulfonation, S-PEEK, S-PSU, PSU-CI, ICVT film, the aryl polymer film, the polyetherketone film, polybenzimidazole membrane, thermoplastic alkaline polymer film, the perfluorinated sulfonic acid polymer film, perfluorocarboxylic acid ester iolon, polymeric amide, polyamine, poly-(vinyl alcohol) film, perfluor phosphonic acid ester film.
5. the method for preparing the one or more described anode architectures in the above claim of a kind of basis,
It is characterized in that
I) allow this film pre-swelling in deionized water,
Ii) this preswollen polymeric film is directly applied to this anode and
Iii) this anode is enclosed in this polymeric film, so that it can not be soaked by catholyte.
According to the one or more described anode architectures in claim 1-4 decorate and mechanicals on the purposes of electrochemical deposition metallic coating.
7. purposes according to claim 6,
It is characterized in that
This decoration and industrial goods are immersed to suitable catholyte, and generate enough electric currents in order to deposit this metallic coating between these goods and this anode.
8. according to claim 6 and/or 7 described purposes,
It is characterized in that
This sedimentation is carried out in the temperature range of 1 ° of C-150 ° of C.
9. according to the one or more described purposes in claim 6-8,
It is characterized in that
Select a kind of can metal refining or the catholyte of metal alloy as catholyte, these metals or metal alloy choosing be silver freely, gold, palladium, platinum, rhodium, ruthenium, iridium, rhenium, copper, tin, zinc, iron, nickel, cobalt, chromium, manganese, molybdenum, tungsten, tantalum, thallium, bismuth, antimony, indium, gallium, lead, cerium, selenium, cadmium, samarium, vanadium, the group of tellurium and their alloy composition.
10. for depositing the electrolyzer of electrolytic coating, comprise a negative electrode, a kind of catholyte and according to the one or more described a kind of anode architectures in claim 1 to 4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010055143.0A DE102010055143B4 (en) | 2010-12-18 | 2010-12-18 | Direct contact membrane anode for use in electrolytic cells |
| DE102010055143.0 | 2010-12-18 | ||
| PCT/EP2011/072191 WO2012080078A2 (en) | 2010-12-18 | 2011-12-08 | Dire-contact membrane anode for use in electrolysis cells |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103429797A true CN103429797A (en) | 2013-12-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800605189A Pending CN103429797A (en) | 2010-12-18 | 2011-12-08 | Dire-contact membrane anode for use in electrolysis cells |
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| Country | Link |
|---|---|
| US (1) | US20130264215A1 (en) |
| JP (1) | JP2013545899A (en) |
| CN (1) | CN103429797A (en) |
| DE (1) | DE102010055143B4 (en) |
| WO (1) | WO2012080078A2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011114931B4 (en) | 2011-10-06 | 2013-09-05 | Umicore Galvanotechnik Gmbh | Process for more selective electrolytic deposition of gold or a gold alloy |
| DE102012004348B4 (en) | 2012-03-07 | 2014-01-09 | Umicore Galvanotechnik Gmbh | Use of organic thiourea compounds to increase the galvanic deposition rate of gold and gold alloys |
| JP5676515B2 (en) * | 2012-04-11 | 2015-02-25 | マテックス・ジャパン株式会社 | Insoluble metal electrode, electrolysis apparatus, and plating method |
| DE102014116717A1 (en) | 2014-11-14 | 2016-05-19 | Maschinenfabrik Kaspar Walter Gmbh & Co Kg | Electrolyte and process for the production of chrome layers |
| CN113383118A (en) | 2019-01-24 | 2021-09-10 | 德国艾托特克公司 | Membrane anode system for electrolytic zinc-nickel alloy deposition |
| CN114787425A (en) | 2019-12-20 | 2022-07-22 | 德国艾托特克有限两合公司 | Method and system for depositing zinc-nickel alloy on substrate |
| DE102022121557A1 (en) | 2022-08-25 | 2024-03-07 | Maschinenfabrik Kaspar Walter Gmbh & Co Kg | METHOD FOR CONTROLLING THE CHROME SUPPLY IN AN ELECTROLYSIS PROCESS FOR PRODUCING CHROME LAYERS AND AN ELECTROLYSIS CELL THEREFOR |
| WO2024073867A1 (en) * | 2022-10-02 | 2024-04-11 | Magneto Special Anodes (suzhou) Co., Ltd. | Electrode and use thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8302640D0 (en) * | 1982-02-17 | 1983-03-02 | Ici Plc | Production of ion-exchange membrane |
| US4778572A (en) * | 1987-09-08 | 1988-10-18 | Eco-Tec Limited | Process for electroplating metals |
| DE4032856A1 (en) * | 1990-10-13 | 1992-04-16 | Schering Ag | MEMBRANE ELECTROLYSIS MODULE |
| EP0574791B1 (en) | 1992-06-13 | 1999-12-22 | Aventis Research & Technologies GmbH & Co. KG | Polymer electrolyte membrane and process for its manufacture |
| DE4314745C1 (en) | 1993-05-04 | 1994-12-08 | Fraunhofer Ges Forschung | Fuel cell |
| JPH10130878A (en) | 1996-11-01 | 1998-05-19 | Asahi Glass Co Ltd | Electrolytic nickel plating method |
| BE1011218A3 (en) | 1997-06-16 | 1999-06-01 | Solvay | PROCESS FOR THE MANUFACTURE OF AN ION EXCHANGE MEMBRANE FOR USE AS A SEPARATOR IN A FUEL CELL. |
| DE10010001A1 (en) | 2000-03-02 | 2001-09-06 | Celanese Ventures Gmbh | Membranes useful in fuel cells comprise a blend of sulfonated aryl polymer, aminated or nitrated polyether(ether)sulfone and plasticizer |
| JP4414819B2 (en) * | 2004-06-23 | 2010-02-10 | 株式会社フルヤ金属 | Partial plating apparatus and partial plating method |
| DE102005018291A1 (en) * | 2005-04-18 | 2006-10-19 | Varta Microbattery Gmbh | The fuel cell system |
| DE102006040749A1 (en) | 2006-08-31 | 2008-03-06 | Daimler Ag | Oxidation-stabilized polymer electrolyte membranes for fuel cells |
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- 2011-12-08 WO PCT/EP2011/072191 patent/WO2012080078A2/en active Application Filing
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- 2011-12-08 JP JP2013543655A patent/JP2013545899A/en active Pending
- 2011-12-08 US US13/994,992 patent/US20130264215A1/en not_active Abandoned
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| US20130264215A1 (en) | 2013-10-10 |
| WO2012080078A3 (en) | 2013-04-25 |
| DE102010055143B4 (en) | 2022-12-01 |
| DE102010055143A1 (en) | 2012-06-21 |
| WO2012080078A4 (en) | 2013-08-01 |
| JP2013545899A (en) | 2013-12-26 |
| WO2012080078A8 (en) | 2013-06-06 |
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